Plasma polymerization of allyl alcohol on polyolefin-based materials: characterization and adhesion properties

Hydroxyl-rich surfaces have been obtained through the plasma polymerization of allyl alcohol on various polyolefin-based substrates. The influence of plasma parameters (deposition time and power), the type of substrate, and water washing on the chemical structure of the formed plasma polymers was investigated. The characterization involved contact angle measurements, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) analyses. To increase the sensitivity of XPS towards hydroxyl groups, derivatization with trifluoroacetic anhydride was performed. In addition, the adhesion between plasma-polymerized layers and a two-component polyurethane lacquer was evaluated by a 90° peel test. It was shown that power had a pronounced influence on both water wettability and hydroxyl group retention, while deposition time mainly influenced the film thickness. A relationship between the extent of hydroxyl functionality and the loss of material during the washing procedure was also found. Furthermore, it was shown that the chemical structure of the plasma polymers was not seriously affected by the choice of substrate. On the contrary, the adhesion properties of the substrates with plasma-polymerized layers were found to be highly dependent on the substrate used. For one of the substrates, the adhesion tests revealed an excellent lacquer adhesion when appropriate process parameters during the plasma deposition were used. The other substrate showed considerably lower peel forces. The difference in adhesion properties between the substrates may be explained as an effect of vacuum-ultraviolet (VUV) emission present during the plasma deposition. The VUV emission is able to create radicals in the near-surface region of the substrate and thereby cause chain scission reactions, lowering the cohesive strength of the substrate. Finally, this study showed that reflection absorption spectroscopy (RAS) is a suitable FTIR technique for obtaining structural information about plasma-polymerized layers thinner than 50 nm.     

Improving the adhesion properties of polypropylene using a liquid-phase sulfonation treatment

This work describes the effects of a stable, short-reaction time, liquid-phase sulfonation technique aimed at improving the adhesion properties of polypropylene. The relationships among SO₃ concentration (0.15, 0.2, and 0.3 N), treatment time, surface chemistry, and adhesion debond strength have been investigated for polypropylene (PP) sheets sulfonated with SO₃ dissolved in 1,1,2-trichloro 1,2,2-trifluoroethane and neutralized using ammonium hydroxide (NH₄OH) or polyethyleneimine (PEI). It was confirmed that PEI neutralized specimens, compared to untreated PP, exhibited a larger increase in debond strength (~269% increase) than similarly treated specimens neutralized with NH₄OH (~210% increase). ATR-FTIR spectroscopy indicates the formation of sulfonic acid, ethylenic, ketone and alcoholic hydroxyl groups. These results are supported by X-ray photoelectron spectroscopy (XPS) that show the O : C ratios increasing from 0.03 to 0.25 for both the NH₄OH and PEI, and the S : C atomic ratios increasing from 0.0 to 0.05 and 0.06 for the NH₄OH and PEI, respectively. Furthermore, XPS examination of PEI neutralized specimens revealed a nitrogenated surface (~6%), providing evidence that PEI had grafted onto the sulfonated surface. The observed increases in adhesion are attributed to formation of polar functionalities and increased wettability (as measured by water contact angle measurements). The neutralizing agent also affects degree of adhesion improvement: the PEI causes larger increases in adhesion compared to the NH₄OH. The physical effects of sulfonation were examined using environmental scanning electron microscopy (ESEM), which showed crack formation after 2 min of treatment. Sulfonation times beyond 5 min degraded the polymer surface (severe microcracking and sloughing of the surface layer) decreasing the adhesion debond strength.     

Plasma‐induced surface modification and adhesion enhancement of polypropylene surface

Unoriented (UPP) and biaxially oriented (BOPP) polypropylene films were treated under radio frequency plasma of air, nitrogen, oxygen, and ammonia. Surface modification of polypropylene films was investigated by using surface energy measurement and attenuated total reflection (ATR)‐FTIR spectroscopy. Surface energy of air and nitrogen plasma‐treated polypropylene film increased for shorter treatment time and then decreased and attained an equilibrium value. Such changes in surface energy were not observed for oxygen and ammonia plasma‐treated polypropylene film, which increased to an equilibrium value. ATR‐FTIR studies revealed characteristic differences in the absorption spectra for short‐duration and long‐duration treatments. From the relative intensity change in the C—H stretching vibration, the mechanism of surface chemical reaction could be inferred. Studies regarding the durability of surface modification due to plasma treatment were evaluated by investigating surface energy of samples aged for 2 months. Treated films subjected to peel strength measurement showed improvement in bondability for UPP and BOPP film by hydrophilic surface modification accompanied by surface crosslinking. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 925–936, 2002     

聚丙烯用附着力促进剂研究进展

从氯化聚丙烯（CPP）的改性、附着力促进剂的无氯化和水性化三个方面综述了聚丙烯（PP）用附着力促进剂的研究进展。介绍了不饱和酸（酐）改性CPP的研究和无氯附着力促进剂的制备方法,阐述了机械法、相反转法、自乳化法和乳液聚合法制备水性附着力促进剂时各自的优缺点和适用范围,总结了可控自由基聚合在PP用附着力促进剂领域的应用。最后指出在进一步的研究中还需要提高无氯附着力促进剂与面漆树脂相容性和水性附着力促进剂的稳定性。     

Effect of molecular structure in branched polyethylene on adhesion properties with polypropylene

Adhesion properties between branched polyethylene (PE) and isotactic polypropylene (PP) were studied by a peel test and scanning electron microscopy. In this study, two types of branched PEs were used; one is a linear low density polyethylene (LLDPE) and the other is a high pressure low density polyethylene (LDPE). The adhesive strength of the LLDPE/PP is much higher than that of LDPE/PP. Furthermore, the formation of PE influxes between PP spherulites has a small effect on the adhesion. The dynamic viscoelastic measurements for the binary blends composed of branched PE and PP were also carried out to estimate the interfacial tension by using a rheological emulsion model proposed by Palierne. The interfacial tension is 1.0 mN for LLDPE/PP and 2.1 mN for LDPE/PP, suggesting that the interfacial thickness of LLDPE/PP is about twice that of LDPE/PP. The adhesive strength between branched PE and PP will be determined by the interfacial thickness, which represents the entanglements between two polymers. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 457–463, 1998     

Dynamic wetting of plasma‐treated polypropylene nonwovens

Various techniques have been employed to improve the wettability of polypropylene materials for a wide range of applications. In this study, polypropylene nonwovens were treated in oxygen plasma for improving water adsorption properties. The effects of plasma treatment on wetting and water adsorption behavior were characterized using dynamic contact angle measurements and dynamic sorption measurements. The introduction of hydrophilic groups was detected by attenuated total reflection–Fourier transform infrared spectroscopy. The plasma treatment roughened the fiber surface revealed by atomic force microscopy. The roughened and hydrophilic surface resulted in the change in advancing and receding contact angles. The dynamic sorption measurements also examined the water adsorption behavior of the materials. The investigation revealed that plasma treatment could significantly improve the water adsorption properties of polypropylene nonwovens. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2157–2160, 2007     

Effect of DC glow discharge treatment on the surface energy and surface resistivity of thin film of polypropylene

A change in the surface energy and surface resistivity of a thin film of polypropylene (PP) of thickness 100 μm was investigated, using direct current (DC) glow discharge. The thin film of the PP was treated for various discharge powers and treatment time and the modification in the surface energy and the surface resistivity was observed. To investigate the modification in the surface energy after DC glow discharge treatment, contact angle of two test liquids formamide and de‐ionized water over the surface of PP film was measured. By measuring the contact angle the change in surface energy and its two polar and dispersive components have been measured. It was observed that at a given power level of DC glow discharge surface energy and its polar component increases with increase of the treatment time, attains a maximum value, and then becomes almost constant. Correspondingly, with increase in surface energy, a decrease in surface resistivity was observed. Also, a change in surface morphology was observed by atomic force microscopy and by FT‐IR spectra generation of polar groups at the surface of PP film. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 767–772, 2007     

Effects of environment and heat treatment on an oxygen plasma-treated polyimide surface and its adhesion to a chromium overcoat

—The effects of oxygen plasma treatment time, duration of storage, and heat treatment on the surface chemistry of and Cr adhesion to Dupont RC5878 and Kapton polyimides were investigated using X-ray photoelectron spectroscopy (XPS), and contact angle and peel strength measurements. The XPS results indicate that the initial stage of plasma treatment involves oxygen adsorption with insignificant modification of the surface chemistry. After 5 s of plasma treatment the surface chemistry is modified, as suggested by the changes in the carbonyl and partially oxidized carbon functional groups' contributions to the C(1s) line shape. These modifications resulted in an increase in the peel strength and a decrease in the contact angle of water. Over the first month of storage, the intensity of the carbonyl functional group peak decreased, while the contact angle increased and reached a steady-state value of 30° after 20 days of storage. These changes are mainly attributed to moisture absorption. Importantly, the metal adhesion to polyimide remained fairly constant over the storage period. The aged plasma-treated surface experienced loss of moisture when baked at 150°C for less than 5 min. This was followed by an increase of the partially oxidized carbon at the expense of the plasma-induced carbon-oxygen bonds at higher baking temperatures or longer times.     

Electrical properties of modified‐grafted polypropylene

The electrical properties of polypropylene (PP), grafted polypropylene (PP‐g‐PVP), and modified‐grafted PVP with α‐cyano‐β‐(2‐thienyl) crotononitrile were investigated. Also, the electrical characteristic of the modified‐grafted PVP subjected to γ‐irradiation (60 kGy) was studied. The results show that the σ of trunk polymer undergoing different degree of grafting generally increases as function of the grafting yield. The grafting yield between 64.1 and 149% resulted in a progressive decrease in ΔE_σ value. Inclusion of sulfur‐containing substrate in different films, having various grafting yields, leads to both increase and decrease in σ values. A significant increase in σ values is observed upon inclusion of sulfur‐containing substrate having maximum grafting yield (149%). These changes are accompanied by fluctuation in σ values. The exposure of sulfur‐containing substrate in grafting film to a dose of 60 kGy results in a significant decrease in ΔE_σ values for the films undergoing a grafting yield between 64.1 and 149%. The observed changes in ΔE_σ of different films investigated could be attributed mainly to corresponding changes in σ values. The observed improvement in electrical properties is mainly because of possible increase in concentration of charge carrier and/or their mobilities. The scanning electron micrographs of some selected films show significant changes in the morphology of the films investigated due to changing the grafting yield, inclusion of sulfur‐containing substrate, and exposure to γ‐irradiation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3797–3803, 2007     

Surface and adhesion properties of poly(ethylene glycol) on polyester(polyethylene terephthalate) fabric surface: Effect of air‐atmospheric plasma treatment

The surface and adhesion properties of different molecular weight poly(ethylene glycol) (PEG) (400, 1500, and 3000 g/mol) on untreated and air‐atmospheric plasma‐treated PET woven fabrics were studied, with the aim of developing durable hydrophilic PET fibrous structures. PEG application was carried out by padding of the PET fabric in aqueous solution of PEG followed by curing and drying. The surface properties of the PEG‐coated PET fabrics were then characterized using wicking test to measure the water contact angle (θ°) and capillary weight (W_c), and using atomic force microscopy (AFM) images in the tapping mode. Results showed that without a prior air‐atmospheric plasma treatment of the PET fabric, the water contact angle decreased and capillary weight increased with the three PEGs, implying an increase in the hydrophilicity of both inner and outer PET fabric fiber surface. Air‐plasma treatment of the PET fabrics before PEG coating increases further the hydrophilicity of the inner fabric fiber surface: the capillary weight was almost doubled in the case of the three PEGs. Best results were obtained with PEG 1500: water contact angle decreasing from 82° to 51°, and the capillary weight increasing from 11 mg to 134 mg. Moreover, wash fastness test at room temperature and at 80°C confirms improved adhesion of PEG‐1500 to the plasma‐treated PET woven fabric surface, while under the same conditions the plasma‐treated PET without PEG loses completely its hydrophilic character. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Surface designing of polypropylene by critical monitoring of the grafting conditions

The grafting of acrylic acid onto electron beam‐irradiated polypropylene was carried out using preirradiation method. The stability of peroxy radicals was investigated by electron spin resonance. It was found that the decay of peroxy radicals is much faster at 70°C than at 40°C and ambient temperature. The grafting has been observed to be strongly dependent on the monomer dilution in the reaction medium. The grafting was ascertained by attenuated total reflectance (ATR). The distribution of grafts across the samples was monitored by infrared microscopy. It was found that the graft management is considerably influenced by composition of the grafting medium. The grafting involving pure monomer leads to the surface enrichment with the polyacrylic acid chains. The samples grafted in pure monomer led to much lower contact angles as compared to the diluted monomer solution. The swelling of the grafted samples also showed a trend that was governed by the graft management. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 546–553, 2006     

Affect of adhesion and properties of kenaf (Hibiscus cannabinus L.) stem in particleboard performance

The objective of this work was to evaluate the adhesion and basic properties of kenaf stem, and its physical and mechanical properties on particleboard panels. In this study, rubberwood (RW) was used as a control. Single-layer experimental panels were produced from whole stem, core, and bast particles of kenaf. Findings revealed that the core part resulted in higher wettability and lower contact angle than the bast. Kenaf bast (KB) gave the highest buffering capacity, while kenaf core (KC) gave the lowest buffering capacity towards acid. The lowest specific gravity was shown by KC followed by kenaf whole stem (KWS) and KB. For particle analysis, KWS gave the highest acceptable particle distribution (73.9%), whilst KC, KB, and RW had particle distributions of 62.5, 68.1, and 56.8%, respectively. Particleboard panels produced from KWS had the highest average values of modulus of rupture and modulus of elasticity with good compaction under scanning electron microscopic. Panels made from bast particles had the lowest mechanical properties among the three types of panels. The internal bonding strengths and dimensional stability of the specimens followed the similar trend above. The results of this study indicate that the specific gravity and adhesion properties of the starting material play a role in determining the physical and mechanical properties of the particleboard panels.     

Wettability and adhesion studies of plasma-treated plastic substrates for gelatin holograms

The feasibility study of using polycarbonate and poly(methyl methacrylate) substrates treated with the oxygen plasma for dichromated gelatin holograms is reported. The contact angles of water on both treated and untreated substrates were measured to indicate the wettability of substrate surfaces. An appreciable increase in adhesion between the dichromated gelatin film and the polycarbonate substrate after the oxygen plasma treatment was demonstrated.     

Wetting and adhesion of water-borne printing inks on surface-modified polyolefins

Polyolefin films were surface-modified by different methods to improve the wetting and adhesion of water-borne printing inks. Polyethylene (PE) films were treated with corona at various energy levels. Surface-modified PE films were characterized by contact angle measurements and electron spectroscopy for chemical analysis (ESCA). Good wetting was already achieved with treatment at a lower energy level. Various degrees of adhesion were obtained at various degrees of treatment. A hydrophilic monomer, 2-hydroxyethylmethacrylate (HEMA), was polymerized onto the surfaces of polypropylene (PP) with radiation-induced grafting, which was carried out at two different radiation doses. In both cases, a thick, visible layer of polyHEMA was formed on the surface of PP, and satisfactory wetting was already achieved at lower radiation doses. Scanning electron microscopy (SEM) showed that different degrees of roughness were achieved at various radiation doses. Like the case of corona-treated PE, different degrees of adhesion were obtained at different degrees of surface treatment. This study shows that improved wetting alone is not satisfactory for good practical adhesion', regardless of the surface modification method used.     

Effects of interfacial adhesion on properties of polypropylene/Wollastonite composites

Wollastonite reinforced polypropylene (PP/CaSiO₃) composites were prepared by melt extrusion. A silane coupling agent and a maleic anhydride grafted PP (PP‐g‐MA) were used to increase the interfacial adhesion between the filler and the matrix. The increased adhesion observed by scanning electron microscopy (SEM) resulted in improved mechanical properties. A model was applied to describe the relationship between the interfacial adhesion and tensile properties of PP/CaSiO₃ composites. There is stronger interfacial adhesion between silane‐treated CaSiO₃ and polymer matrix containing PP‐g‐MA as a modifier. Results of dynamic mechanical thermal analysis (DMTA) showed that stronger interfacial adhesion led to higher storage modulus. The influence of CaSiO₃ particles on the crystallization of PP was studied by using differential scanning calorimetry (DSC). The introduction of CaSiO₃ particles does not affect the crystallization temperature and crystallinity of PP matrix significantly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Adhesion characteristics of plasma-treated polypropylene to mild steel

The ability of polypropylene (PP) to adhere to mild steel depends to a large extent on the surface characteristics of both PP and steel. The adhesion of PP was improved by treatment in a cold plasma from oxidizing gases (O₂, H₂O, etc.). This surface functionalization was followed ex situ by means of contact angle measurements and XPS (X-ray photelectron spectroscopy) analysis. The polymer/steel assembly was fabricated by hot-pressing in vacuum, or after exposure to ambient air. Adhesion to steel, as determined by the lap-shear test, increased when the PP was treated with Ar-containing plasma gas and joined to steel after exposure to room atmosphere. Correlations between the polarity, the atomic (O/C, N/C) ratio, the dispersive component of the surface energy, and the degree of PP/steel adhesion are discussed.     

Structure and properties of rubber-modified polypropylene impact blends

The state of dispersion of poly(ethylene-co-propylene) (PEP) rubber and high-density polyethylene (HDPE) in polypropylene (PP) blends was investigated using scanning electron microscopy to examine solvent-etched microtomed surfaces cut at low temperatures. The validity of the method was established by comparing the areal fraction of dispersed particles in micrographs with the volume fraction of PEP and HDPE in PP-rich blends. When small amounts of PEP and HDPE were added to PP, they combined to form composite PEP–HDPE particles with characteristic internal structures in a PP matrix. Changes in impact strength and flexural modulus with changes in mixing conditions and blend composition were determined and interpreted in terms of the size, composition, and internal structure of the dispersed particles. Particle growth in the melt limited the impact strength level achieved in molded articles. A simple model proposed for screening rubbers for toughening of brittle plastics successfully predicts that PEP rubber should be an excellent impact modifier for PP.     

Modifying adhesion of linear low‐density polyethylene to polypropylene by blending with a homogeneous ethylene copolymer

Adhesion of a Ziegler–Natta catalyzed ethylene copolymer (ZNPE) to polypropylene (PP) was studied by measuring the delamination toughness G of coextruded microlayers by using the T‐peel test. Low values of G compared to a homogeneous copolymer with approximately the same short chain branch (SCB) content were attributed to an amorphous interfacial layer of low molecular weight, highly branched ZNPE fractions. Blending ZNPE with a homogeneous metallocene catalyzed copolymer (mPE) increased G. In this regard, mPE with higher SCB content was more effective than mPE with slightly lower SCB content. The ZNPE interface was mimicked by microlayering ZNPE and ZNPE blends with polystyrene from which the ZNPE layers were easily separated without damage to the surface. Examination with atomic force microscopy revealed a soft coating about 8 nm thick on the surface of the ZNPE layer. Blending with mPE reduced or eliminated the amorphous interfacial layer. It was proposed that mPE increased miscibility of low molecular weight, highly branched fractions of ZNPE and prevented their segregation at the interface. After blending with mPE eliminated the interfacial layer, G increased to a value comparable to that of a homogeneous copolymer with about the same SCB content as ZNPE bulk chains. The increase in G was attributed to epitaxial crystallization of the ethylene copolymer in the absence of an amorphous interfacial layer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 109–115, 2004     

竹材表面处理对胶合性能的影响

为提高竹材的胶合性能,用自制的偶联剂对竹材表面进行预处理,测试了处理前后表面接触角的变化,从而计算出竹篾外表面自由能及其分量的变化。将处理的竹篾压制成竹篾层积材,测试了竹篾层积材的物理及力学性能,并与未处理竹篾层积材进行了比较。研究结果表明,经偶联剂处理的竹篾表面自由能提高,压制的竹篾层积材的胶合强度也有明显的提高,还对偶联剂处理前后强度变化的原因进行了探讨。